JPH0239450B2 - - Google Patents
Info
- Publication number
- JPH0239450B2 JPH0239450B2 JP57167958A JP16795882A JPH0239450B2 JP H0239450 B2 JPH0239450 B2 JP H0239450B2 JP 57167958 A JP57167958 A JP 57167958A JP 16795882 A JP16795882 A JP 16795882A JP H0239450 B2 JPH0239450 B2 JP H0239450B2
- Authority
- JP
- Japan
- Prior art keywords
- tin oxide
- powder
- oxide film
- substrate
- particle size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 33
- 229910001887 tin oxide Inorganic materials 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 28
- 239000002245 particle Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000758 substrate Substances 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 description 15
- 150000003606 tin compounds Chemical class 0.000 description 10
- NGDPCAMPVQYGCW-UHFFFAOYSA-N dibenzothiophene 5-oxide Chemical compound C1=CC=C2S(=O)C3=CC=CC=C3C2=C1 NGDPCAMPVQYGCW-UHFFFAOYSA-N 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000002019 doping agent Substances 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- JTRGWAAQOVTJGY-UHFFFAOYSA-L [dibutyl-(2,2,2-trifluoroacetyl)oxystannyl] 2,2,2-trifluoroacetate Chemical compound CCCC[Sn](CCCC)(OC(=O)C(F)(F)F)OC(=O)C(F)(F)F JTRGWAAQOVTJGY-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HCTWPOYNWRYAMR-UHFFFAOYSA-L dipropyltin(2+);2,2,2-trifluoroacetate Chemical compound FC(F)(F)C(=O)O[Sn](CCC)(CCC)OC(=O)C(F)(F)F HCTWPOYNWRYAMR-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910017855 NH 4 F Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- -1 organic acid compound Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/211—SnO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/17—Deposition methods from a solid phase
Description
【発明の詳細な説明】
本発明はガラス、セラミツク、金属等の基体に
酸化錫膜を形成する方法に関し、更に詳しくは高
温のガラス、セラミツク、または金属等の基体表
面に有機錫化合物の粉末を接触させることによ
り、基体表面に酸化錫を形成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for forming a tin oxide film on a substrate such as glass, ceramic, metal, etc., and more specifically to a method of forming an organic tin compound powder on the surface of a substrate such as high temperature glass, ceramic, or metal. The present invention relates to a method of forming tin oxide on a substrate surface by contacting the substrate.
一般に、酸化錫膜はすぐれた硬度を有している
ことからビン製品・食器などの表面の傷つき防止
に広く用いられている。また酸化錫膜の半導体的
性質を利用した広用例も多く、例えば酸化錫膜を
形成したガラスは液晶セルの電極板・防曇ガラス
などの透明な電導体としての用途に広く使用され
ており、酸化錫膜を有するセラミツクス薄板は抵
抗体など電気部品としても極めて有用である。更
には酸化錫膜の赤外線反射特性を利用し、ガラス
あるいは金属管上に酸化錫膜を形成させたもの
が、それぞれ太陽熱集熱器のカバーガラス、太陽
熱集熱管として用いられている。 In general, tin oxide films have excellent hardness and are therefore widely used to prevent scratches on the surfaces of bottle products, tableware, etc. In addition, there are many widespread applications that utilize the semiconducting properties of tin oxide films; for example, glass on which tin oxide films are formed is widely used as transparent conductors such as electrode plates of liquid crystal cells and anti-fog glass. Ceramic thin plates with tin oxide films are also extremely useful as electrical components such as resistors. Furthermore, by utilizing the infrared reflective properties of a tin oxide film, a tin oxide film formed on a glass or metal tube is used as a cover glass for a solar heat collector and a solar heat collection tube, respectively.
酸化錫膜をガラス・セラミツクスまたは金属等
の基体表面に形成させる方法には種々あるが、量
産に適した方法として古くから四塩化錫を有機溶
媒に溶かした溶液を高温状態にある前記の基体の
表面に吹付ける方法が用いられてきた。そして近
年、四塩化錫またはジメチル二塩化錫を加熱蒸発
させて得られる蒸気を高温のガラス、セラミツク
スまたは金属等の基体表面に接触させるいわゆる
CVDも広く採用されている。 There are various methods for forming a tin oxide film on the surface of a substrate such as glass, ceramics or metal, but a method suitable for mass production has long been used to form a solution of tin tetrachloride in an organic solvent on the substrate at a high temperature. Surface spraying methods have been used. In recent years, so-called so-called
CVD is also widely adopted.
更にこれらに代る方法として有機酸化合物の粉
末を直接高温のガラス表面に吹付けることから成
る酸化錫膜の形成方法（以下粉末法）も試みられ
ている。 Furthermore, as an alternative to these methods, a method of forming a tin oxide film (hereinafter referred to as a powder method) has also been attempted, which consists of directly spraying powder of an organic acid compound onto a hot glass surface.
粉末法は細く粉砕した粉末状有機錫化合物を浮
遊懸濁させた空気またはその他の気体を高温のガ
ラス表面と接触させもので、溶融スプレー法・
CVD法に比べ被膜形成速が速く量産能力にすぐ
れているのが特徴である。通常、粉末状有機錫化
合物としてはジブチル錫オキサイド
〔（C4H9）2SnO以下DBTOとする〕が多く試みら
れ、この場合得られる酸化錫膜の電導性を高める
ためドーパントとして弗化水素ガスが前記粉末懸
濁気流中に加えられる。 The powder method involves contacting air or other gas in which finely ground powdered organotin compounds are suspended with a hot glass surface.
Compared to the CVD method, this method is characterized by faster film formation speed and superior mass production capacity. Usually, dibutyltin oxide [hereinafter referred to as (C 4 H 9 ) 2 SnO, DBTO] is often used as a powdered organic tin compound, and in this case, hydrogen fluoride gas is used as a dopant to increase the conductivity of the resulting tin oxide film. is added to the powder suspension stream.
また、ドーパントとして弗化アンモニウム〔以
下NH4Fとする〕または酸性弗化アンモニウムを
用い、これらの粉末と粉末有機錫化合物の混合粉
末を酸化錫膜形成の出発物質とする方法も提案さ
れている。しかしながらこのような種々の試みに
もかかわらず大面積の防曇用ガラス・太陽電池の
電極ガラスにおいては更に電導性にすぐれた酸化
錫膜が要求されている。 Additionally, a method has been proposed in which ammonium fluoride (hereinafter referred to as NH 4 F) or acidic ammonium fluoride is used as a dopant, and a mixed powder of these powders and a powdered organic tin compound is used as the starting material for forming a tin oxide film. . However, despite these various attempts, tin oxide films with even better conductivity are required for large-area antifogging glasses and electrode glasses for solar cells.
本発明者らは酸化錫膜の電気抵抗に関し鋭意研
究の結果、出発物質である有機錫化合物の粉末よ
り粒子径が10μｍに満たない微粒子を除去するこ
とで得られる酸化錫膜の電導性が向上することを
見い出した。すなわち本発明は加熱した基体に有
機錫化合物の粉末を接触させて、熱分解酸化反応
により基体に酸化錫膜を形成する方法において該
有機錫化合物の粉末の粒子が10μｍ乃至60μｍで
あつて、且つ10μｍ未満の粒径の有機錫化合物を
含まないことを特徴とする基体に酸化錫膜を形成
する方法である。 As a result of intensive research into the electrical resistance of tin oxide films, the present inventors found that the conductivity of tin oxide films obtained by removing fine particles with a particle size of less than 10 μm from the starting material, organic tin compound powder, was improved. I found something to do. That is, the present invention provides a method for forming a tin oxide film on a substrate by a thermal decomposition oxidation reaction by contacting powder of an organotin compound with a heated substrate, wherein the particles of the powder of the organotin compound are 10 μm to 60 μm, and This is a method for forming a tin oxide film on a substrate, characterized in that it does not contain an organic tin compound with a particle size of less than 10 μm.
本発明は有機錫化合物としてジブチル錫オキサ
イド、ジプロピル錫ジトリフルオロアセテート
〔（C3H7）2Sn（CF3COO）2〕又はジブチル錫ジトリ
フルオロアセテート〔（C4H9）2Sn（CF3COO）2）〕
等が用いられるのが好ましく、これらの有機錫化
合物は含水率が１％以下、望ましくは0.5％以下
となるまで乾燥された後、粒径3μｍ乃至60μｍに
なるように粉砕され、分級機により粒径が10μｍ
に満たない微粒子が除去される。 The present invention uses dibutyltin oxide, dipropyltin ditrifluoroacetate [(C 3 H 7 ) 2 Sn (CF 3 COO) 2 ] or dibutyltin ditrifluoroacetate [(C 4 H 9 ) 2 Sn (CF 3 ) as an organic tin compound. COO） 2 ）〕
These organic tin compounds are dried until the moisture content is 1% or less, preferably 0.5% or less, and then ground to a particle size of 3 μm to 60 μm, and then granulated using a classifier. Diameter is 10μm
Particulates less than 100% are removed.
このようにして調整された有機錫化合物の粉末
はキヤリヤーガス中に浮遊懸濁され、次いで該有
機錫化合物の粉末の懸濁気流は350℃以上、望ま
しくは500℃以上に加熱された基体に接触せしめ
られ、該基体表面に酸化錫膜が形成される。 The organotin compound powder prepared in this way is suspended in a carrier gas, and then the suspended air stream of the organotin compound powder is brought into contact with a substrate heated to 350°C or higher, preferably 500°C or higher. A tin oxide film is formed on the surface of the substrate.
この有機錫化合物の粉末を懸濁するキヤリヤー
ガス中には得られる酸化錫膜の電導性を高めるた
めのドーパントとして弗化水素ガスを加えること
ができる。またこのドーパントとして弗化アンモ
ニウムまたは酸性弗化アンモニウムの粉末を有機
錫化合物の粉末に混入させることもできる。 Hydrogen fluoride gas can be added to the carrier gas in which the organic tin compound powder is suspended as a dopant to increase the electrical conductivity of the resulting tin oxide film. Further, ammonium fluoride or acidic ammonium fluoride powder can be mixed into the organotin compound powder as the dopant.
また本発明は基体としてガラス、セラミツク、
金属等が用いられ、それらの形状は板状体、管状
体のものが用いられる。 Further, the present invention uses glass, ceramic,
A metal or the like is used, and the shape thereof is a plate-like body or a tubular body.
本発明によれば、10μｍ未満の粒径の有機錫化
合物を含まない10μｍ乃至60μｍの粒径の有機錫
化合物の粉末を用いることにより、ヘイズのない
電気電導度の大なる透明酸化錫膜を形成できる。
10μｍ乃至60μｍの粒径の有機錫化合物の粉末を
用いるとヘイズのない電気伝導度の大なる透明酸
化錫膜を形成できるかについては定かではない
が、径の微細な10μｍ未満の有機錫化合物の粉末
を含まないため基体表面で熱分解による酸化錫膜
を形成するスピードが早すぎず適当になり、酸化
錫膜の結晶が比較的大きく成長して電気伝導度の
高い膜を形成でき、また60μｍを超える径の大な
る有機錫化合物の粉末を含まないので、キヤリヤ
ーガスに均一に浮遊できるので均一な膜の形成が
容易となり、また膜中に未分解の有機錫化合物が
残らないためヘイズのない透明な酸化錫膜を形成
できるものと推測される。 According to the present invention, a transparent tin oxide film with high electrical conductivity without haze is formed by using powder of an organic tin compound with a particle size of 10 μm to 60 μm, which does not contain an organic tin compound with a particle size of less than 10 μm. can.
It is not certain whether a transparent tin oxide film with high electrical conductivity and no haze can be formed using organotin compound powder with a particle size of 10 μm to 60 μm. Since it does not contain powder, the speed at which a tin oxide film is formed by thermal decomposition on the surface of the substrate is not too fast and appropriate, and the crystals of the tin oxide film can grow relatively large to form a film with high electrical conductivity. Since it does not contain large organotin compound powders with diameters exceeding It is assumed that a tin oxide film can be formed.
また本発明によれば有機錫化合物としてジブチ
ル錫オキサイド、ジプロピル錫ジトリフルオロア
セテート又はジブチル錫ジトリフルオロアセテー
トを用いれば電気伝導度の一層高い酸化錫膜の形
成ができる。 According to the present invention, a tin oxide film with even higher electrical conductivity can be formed by using dibutyltin oxide, dipropyltin ditrifluoroacetate, or dibutyltin ditrifluoroacetate as the organotin compound.
また本発明によれば有機錫化合物の含水率を１
％以下、好ましくは0.5％以下にすることにより、
キヤリヤーガス中にその粉末を均一に浮遊させる
ことができ容易となり、ひいては均一な酸化錫膜
の形成ができる。 Further, according to the present invention, the water content of the organotin compound is reduced to 1
% or less, preferably 0.5% or less,
The powder can be uniformly suspended in the carrier gas, making it easy to form a uniform tin oxide film.
以下に本発明の実施例を説明する。 Examples of the present invention will be described below.
DBTO粉末を含水率0.4％となるまで熱風循環
乾燥機で乾燥した後、粉砕機で粉砕した。この時
のDBTO粉末の粒径は3μｍ乃至60μｍに分布し、
平均粒径は23μｍであつた。次にこのDBTO粉末
を分級機で分級し、粒径が10μｍ未満の粒子を除
去して10μｍ乃至60μｍに分布した平均粒径が27μ
ｍのDBTO粉末を用意した。次いでこのDBTO
粉末をサンドブラストガンに供給し、弗化水素を
含む高圧空気で575〜580℃のガラス表面に吹付け
た。この時、DBTO粉末の供給量は、12ｇ／分
で、吹付け時間を２〜４秒間の範囲で変えること
により膜厚2000〜4000Aの酸化錫膜をガラス表面
に形成させた。なお、この時のガラス厚味は３
mm、寸法15cm×15cmであり、吹付に用いた高圧空
気は圧力4.0Kg／cm2、流量は100／分であつた。
また弗化水素ガスの高圧空気への混入量は空気中
弗素量とDBTO中の錫との比率、すなわちＦ／
Snで2.0となるようにした。得られた酸化錫膜の
電気抵抗を測定した後、膜厚をタリサーフで測定
した。被膜の電気抵抗と膜厚の関係を第１図に実
線で示した。次に比較例を得るため粒径が3μｍ
乃至60μｍに分布し、平均粒径が23μｍの分級し
ないDBTO粉末を前記と同じサンドブラストガ
ンに供給し、前記と全く同様の方法でガス表面に
吹付け、ガラス表面に酸化錫膜を付着した。この
被膜の電気抵抗と膜厚の関係を第１図に破線で示
した。 The DBTO powder was dried in a hot air circulation dryer until the moisture content was 0.4%, and then ground in a grinder. The particle size of the DBTO powder at this time is distributed from 3μm to 60μm,
The average particle size was 23 μm. Next, this DBTO powder was classified with a classifier to remove particles with a particle size of less than 10 μm, and the average particle size was 27 μm, which was distributed from 10 μm to 60 μm.
m DBTO powder was prepared. Then this DBTO
The powder was fed into a sandblasting gun and blasted onto the glass surface at 575-580°C with high pressure air containing hydrogen fluoride. At this time, the amount of DBTO powder supplied was 12 g/min, and the spraying time was varied in the range of 2 to 4 seconds to form a tin oxide film with a thickness of 2000 to 4000 A on the glass surface. In addition, the glass thickness at this time is 3
mm, dimensions 15 cm x 15 cm, and the high pressure air used for spraying had a pressure of 4.0 Kg/cm 2 and a flow rate of 100/min.
In addition, the amount of hydrogen fluoride gas mixed into high-pressure air is determined by the ratio of the amount of fluorine in the air to the tin in DBTO, that is, F/
The Sn value was set to 2.0. After measuring the electrical resistance of the obtained tin oxide film, the film thickness was measured using Talysurf. The relationship between the electrical resistance and film thickness of the film is shown in FIG. 1 by a solid line. Next, to obtain a comparative example, the particle size was 3 μm.
Unclassified DBTO powder having a particle size distribution of 23 μm to 60 μm was supplied to the same sandblasting gun as above, and was blown onto the gas surface in exactly the same manner as above to deposit a tin oxide film on the glass surface. The relationship between the electrical resistance and film thickness of this film is shown in FIG. 1 by a broken line.
第１図から明らかなように本発明により形成さ
れる酸化錫膜の電導性が比較例のものより向上し
ている。 As is clear from FIG. 1, the electrical conductivity of the tin oxide film formed according to the present invention is improved compared to that of the comparative example.
第１図は酸化錫膜の膜厚と被膜の電気抵抗との
関係を示す図である。
FIG. 1 is a diagram showing the relationship between the thickness of the tin oxide film and the electrical resistance of the film.
Claims (1)
せて、熱分解酸化反応により基体に酸化錫膜を形
成する方法において、該有機錫化合物の粉末の粒
径が10μｍ乃至60μｍであつて、且つ10μｍ未満の
粒径の有機錫化合物を含まないことを特徴とする
基体に酸化錫膜を形成する方法。1. A method of forming a tin oxide film on the substrate by a thermal decomposition oxidation reaction by bringing an organotin compound powder into contact with a heated substrate, wherein the organotin compound powder has a particle size of 10 μm to 60 μm, and 10 μm. A method for forming a tin oxide film on a substrate, characterized in that it does not contain an organotin compound having a particle size of less than
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16795882A JPS5957914A (en) | 1982-09-27 | 1982-09-27 | Formation of tin oxide film on substrate |
| ES525935A ES8507628A1 (en) | 1982-09-27 | 1983-09-26 | Process for coating a substrate with a tin oxide layer. |
| DE8383401875T DE3369118D1 (en) | 1982-09-27 | 1983-09-26 | Process for coating a substrate with a tin oxide layer |
| EP19830401875 EP0106744B1 (en) | 1982-09-27 | 1983-09-26 | Process for coating a substrate with a tin oxide layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16795882A JPS5957914A (en) | 1982-09-27 | 1982-09-27 | Formation of tin oxide film on substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5957914A JPS5957914A (en) | 1984-04-03 |
| JPH0239450B2 true JPH0239450B2 (en) | 1990-09-05 |
Family
ID=15859193
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16795882A Granted JPS5957914A (en) | 1982-09-27 | 1982-09-27 | Formation of tin oxide film on substrate |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0106744B1 (en) |
| JP (1) | JPS5957914A (en) |
| DE (1) | DE3369118D1 (en) |
| ES (1) | ES8507628A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2706462B1 (en) * | 1993-06-17 | 1995-09-22 | Saint Gobain Vitrage Int | Organo-metallic powdery compounds intended to form a layer of tin oxide on a substrate, process for using it and substrate thus coated. |
| JP3796069B2 (en) * | 1999-07-15 | 2006-07-12 | 三洋電機株式会社 | Solar cell module |
| US20100126227A1 (en) * | 2008-11-24 | 2010-05-27 | Curtis Robert Fekety | Electrostatically depositing conductive films during glass draw |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52919A (en) * | 1975-06-24 | 1977-01-06 | Nippon Sheet Glass Co Ltd | Method of depositing thin film of metallic oxide on glass surface |
| JPS56134538A (en) * | 1980-03-15 | 1981-10-21 | Nippon Sheet Glass Co Ltd | Application of tin oxide layer doped by halogen, especially by fluorine to glass surface by pyrolysis |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2380997A1 (en) * | 1977-02-16 | 1978-09-15 | Saint Gobain | PROCESS FOR MANUFACTURING HEAT PROTECTING GLAZING |
| FR2391966A1 (en) * | 1977-05-23 | 1978-12-22 | Saint Gobain | Coating glass with metal oxide - to impart antistatic properties, for use in cockpits |
| JPS5663844A (en) * | 1979-10-31 | 1981-05-30 | Nippon Sheet Glass Co Ltd | Forming method of metal oxide coat |
-
1982
- 1982-09-27 JP JP16795882A patent/JPS5957914A/en active Granted
-
1983
- 1983-09-26 EP EP19830401875 patent/EP0106744B1/en not_active Expired
- 1983-09-26 ES ES525935A patent/ES8507628A1/en not_active Expired
- 1983-09-26 DE DE8383401875T patent/DE3369118D1/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52919A (en) * | 1975-06-24 | 1977-01-06 | Nippon Sheet Glass Co Ltd | Method of depositing thin film of metallic oxide on glass surface |
| JPS56134538A (en) * | 1980-03-15 | 1981-10-21 | Nippon Sheet Glass Co Ltd | Application of tin oxide layer doped by halogen, especially by fluorine to glass surface by pyrolysis |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0106744B1 (en) | 1987-01-14 |
| ES525935A0 (en) | 1985-09-01 |
| JPS5957914A (en) | 1984-04-03 |
| DE3369118D1 (en) | 1987-02-19 |
| ES8507628A1 (en) | 1985-09-01 |
| EP0106744A1 (en) | 1984-04-25 |
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